Hydrogen peroxide, H₂O₂, (in a dilute aqueous solution) is a familiar inhabitant of the medicine cabinet, but there is another more elusive molecule, water oxide, or oxywater, that has the same molecular formula as hydrogen peroxide. Water oxide differs from hydrogen peroxide only by the position of a proton:

Theoreticians have believed for some time that water oxide should be observable. Don’t expect anyone to present you with a bottle of the stuff, though. It is predicted to be less stable than hydrogen peroxide by a whopping 47 kcal mol^-1 (144 kJ mol^-1) in the gas phase. This means that the equilibrium constant for the conversion of hydrogen peroxide into water oxide is a minuscule 10^-35. Furthermore, the rate of oxywater’s conversion into hydrogen peroxide is predicted to be extremely large.

Because of water oxide’s instability, chemists must resort to indirect methods for its detection. Detlef Schroder and his colleagues at the Technical University of Berlin have obtained evidence by mass spectrometry for the fleeting existence of water oxide (1).

Aside from the general interest in elusive molecules, some impetus for investigating oxywater comes from the possible role of oxywater as an intermediate in both biological and abiological oxygen transfer from hydrogen peroxide. Most theoretical studies of oxywater, as well as this experimental study, deal with gas-phase oxywater. Oxywater in aqueous solution, however, is probably considerably more stable relative to hydrogen peroxide. This increased stability increases the likelihood of its involvement in chemical processes in aqueous solution.

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